Manufacture of side-chain aromatic compounds



Patented May 22,1925. 1 i

UNITED, STATES ra'rrl.=zl-r r OFFICE.

rmz GUNTEIB, .O I LUDWIGsHLIEN-ON-THE-B HINE, GEBHANY, ASSIGNOR TO GMSSILLI DYESTOFI CORPORATION, OF NEW YOBK,.'N. Y., A. COBPOBATTON OI nmwaar.

mUl'AOTUBE OI SIDE-CHAIN ABOIATIO COHIOUNDS.

Io Drawing. Application filed larch 2, 1927, Serial No. 72,210, and in Germany larch 8, 1928.

I have found that aromatic compounds, .alkylated, aralkylated or cycloalkylated in the nucleus, may be obtained by treating aromatic compounds with'acid sulfuric acid esl5 ters of alcohols having 3 or more carbon atoms in the molecule, with or without the use of condensing agents. If'the operation be carried out energetically, i. e. with a-lar e quantity of sulfuric acid or at comparative y high tem eratures or with both these GOIldltions, su fonation of the aromatic compounds may take place at the same time.

The process according to the present invention is applicable to all kinds of aromatic 1 compounds. Such compounds may belong to the carbocyclic as well as to the hetergoyclic series, and they may be mono or polynuclear compounds. Hydrocarbons as well as derivatives thereof may be employed. As exam ples of suitable aromatic compounds, benzene and its homologues such as toluene or xylene, naphthalene, anthracene and their homologues, the phenols and naphthols, pyridine, quinoline and the like may be men- 2 tioned. The reaction may be carried outwith all kinds of aliphatic, aromatic-aliphatic or hydroaromatic alcoholshaving at least 3 carbon atoms in their molecule.

' The following examples will further illusso trate how the said invention may be carried out in practice, but the invention is not limited to these examples. The parts are by weight.

Example 1.

296 parts of normal-butyl alcohol are converted into the acid sulfuric acid butyl ester by means of 480 parts of chlorsulfonic acid. The resulting ester is then mixed with .40 256 parts of naphthalene, and the mixture is fofiic acid being converted into the sodium sa The normal-butyl alcohol may be replaced by other butyl alcohols, and also by the propyl alcohols, amyl alcohols cyclohexanol or its homologues and the like. A smaller amount (say one-half) of the sulfuric ester of butyl may also be taken, inhivhich case it is often advantageous to add sulfuric acid.

Example 2.

150 parts of isopropyl alcohol are converted into the acid sulfuric acid propyl ester by means of 290 parts of chlorsulfonic acid. The said ester is added at about 20? C. to 195 parts of benzene. The reaction is complete, after the mixture has been stirred for.several days at about 20 to 30 C. The product is poured on ice and the oily layer formed separated from the aqueous layer. The oil is boiled with an excess of strong caustic soda solution and then' distilled with steam. The resultin distillate is freed from water and subjecte to fractional distillat1on The resultin products have a higher boihng point than enzene and are probably propylated benzenes.

' Emample 3.

195 parts of benzene are mixed with the acidsulfuric acid propyl ester prepared at about 20 C. from 150 parts of isopropyl alcohol and 290 'parts of chlorsulfonic acid. The mixture is stirred for some hours at to C. 300 parts of sulfuric acid of 66 B. strength are then added and after some compounds containing side-chains which consists in acting on an aromatic compound with an acid sulfuric acid ester of an alcohol containing at least 3 carbon atoms.

2. The process of producing aromatic compounds containing side-chains which consists in act on an aromatic compound with an acid sulfuric acid ester of an alwitli' acid ic acid ester of an alcohol containing at least 3 carbon atoms in coho '-=contain1ng at least 3 carbon atoms in the presence of sulfuric acid. 10 the presence of a condensin agent. In testimony whereof I have hereunto set 5 3. The process of pro ucing aromatic my hand.

compounds containing side-chains which consists in acting on an aromatic compound FRITZ GUNTHER. 

